Growth of graphene from solid carbon sources

Journal name:
Nature
Volume:
468,
Pages:
549–552
Date published:
DOI:
doi:10.1038/nature09579
Received
Accepted
Published online

Monolayer graphene was first obtained1 as a transferable material in 2004 and has stimulated intense activity among physicists, chemists and material scientists1, 2, 3, 4. Much research has been focused on developing routes for obtaining large sheets of monolayer or bilayer graphene. This has been recently achieved by chemical vapour deposition (CVD) of CH4 or C2H2 gases on copper or nickel substrates5, 6, 7. But CVD is limited to the use of gaseous raw materials, making it difficult to apply the technology to a wider variety of potential feedstocks. Here we demonstrate that large area, high-quality graphene with controllable thickness can be grown from different solid carbon sources—such as polymer films or small molecules—deposited on a metal catalyst substrate at temperatures as low as 800°C. Both pristine graphene and doped graphene were grown with this one-step process using the same experimental set-up.

At a glance

Figures

  1. Synthetic protocol, spectroscopic analysis and electrical properties of PMMA-derived graphene.
    Figure 1: Synthetic protocol, spectroscopic analysis and electrical properties of PMMA-derived graphene.

    a, Monolayer graphene is derived from solid PMMA films on Cu substrates by heating in an H2/Ar atmosphere at 800°C or higher (up to 1,000°C). b, Raman spectrum (514nm excitation) of monolayer PMMA-derived graphene obtained at 1,000°C. See text for details. c, Room temperature IDSVG curve from a PMMA-derived graphene-based back-gated FET device. Top inset, IDSVDS characteristics as a function of VG; VG changes from 0V (bottom) to −40V (top). Bottom inset, SEM (JEOL-6500 microscope) image of this device where the PMMA-derived graphene is perpendicular to the Pt leads. IDS, drain–source current; VG, gate voltage; VDS, drain–source voltage. d, SAED pattern of PMMA-derived graphene. eg, HRTEM images of PMMA-derived graphene films at increasing magnification. In g, black arrows indicate Cu atoms.

  2. Controllable growth of pristine PMMA-derived graphene films.
    Figure 2: Controllable growth of pristine PMMA-derived graphene films.

    a, Difference in Raman spectra from PMMA-derived graphene samples with controllable thicknesses derived from different flow rates of H2. b, The ultraviolet–visible absorption spectra of monolayer graphene and bilayer graphene; peaks are labelled with wavelength of maximum absorption, and value of maximum absorption. The UV transmittance (T in %) is measured at 550nm. c, Raman spectra of graphene derived from sucrose, fluorene and PMMA. d, HRTEM picture of PMMA-derived graphene grown on a Ni film. The PMMA-derived graphene was 3–5 layers thick at the edges.

  3. Spectroscopic analysis and electrical properties of pristine and N-doped PMMA-derived graphene.
    Figure 3: Spectroscopic analysis and electrical properties of pristine and N-doped PMMA-derived graphene.

    a, XPS analysis from the C 1s peak of PMMA-derived graphene (black) and N-doped PMMA-derived graphene (red); the shoulder can be assigned to the C–N bond. b, XPS analysis, showing the N 1s peak (black line) and its fitting (squares), of N-doped PMMA-derived graphene. The atomic concentration of N for this sample is about 2% (C is 98%). No N 1s peak was observed for pristine PMMA-derived graphene. c, Raman spectra of pristine and N-doped PMMA-derived graphene. d, Room temperature IDSVG curves (VDS = 500mV) showing n-type behaviour obtained from three different N-doped graphene-based back-gated FET devices.

References

  1. Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666669 (2004)
  2. Geim, A. K. & Novoselov, K. S. The rise of graphene. Nature Mater. 6, 183191 (2007)
  3. Novoselov, K. S. et al. Two-dimensional gas of massless Dirac fermions in graphene. Nature 438, 197200 (2005)
  4. Ruoff, R. S. Graphene: Calling all chemists. Nature Nanotechnol. 3, 1011 (2008)
  5. Reina, A. et al. Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. Nano Lett. 9, 3035 (2009)
  6. Li, X. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 13121314 (2009)
  7. Kim, K. S. et al. Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 457, 706710 (2009)
  8. Lin, Y. et al. Operation of graphene transistors at gigahertz frequencies. Nano Lett. 9, 422426 (2009)
  9. Lin, Y. et al. 100-GHz transistors from wafer-scale epitaxial graphene. Science 327, 662 (2010)
  10. Schedin, F. et al. Detection of individual gas molecules adsorbed on graphene. Nature Mater. 6, 652655 (2007)
  11. Stankovich, S. et al. Graphene-based composite materials. Nature 442, 282286 (2006)
  12. Stoller, M. D. et al. Graphene-based ultracapacitors. Nano Lett. 8, 34983502 (2008)
  13. Schlapbach, L. & Züttel, A. Hydrogen-storage materials for mobile applications. Nature 414, 353358 (2001)
  14. Hernandez, Y. et al. High-yield production of graphene by liquid-phase exfoliation of graphite. Nature Nanotechnol. 3, 563568 (2008)
  15. Stankovich, S. et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphene oxide. Carbon 45, 15581565 (2007)
  16. Berger, C. et al. Electronic confinement and coherence in patterned epitaxial graphene. Science 312, 11911196 (2006)
  17. Zheng, M. et al. Metal-catalyzed crystallization of amorphous carbon to graphene. Appl. Phys. Lett. 96, 063110 (2010)
  18. Li, X. et al. Chemically derived, ultrasmooth graphene nanoribbon semiconductors. Science 319, 12291232 (2008)
  19. Panchakarla, L. S. et al. Synthesis, structure, and properties of boron- and nitrogen-doped graphene. Adv. Mater. 21, 47264730 (2009)
  20. Wang, X. et al. N-doping of graphene through electrothermal reactions with ammonia. Science 324, 768771 (2009)
  21. Wei, D. et al. Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties. Nano Lett. 9, 17521758 (2009)
  22. Ci, L. et al. Atomic layer of hybridized boron nitride and graphene domains. Nature Mater. 9, 430435 (2010)
  23. Rao, C. N. R. et al. Some novel attributes of graphene. J. Phys. Chem. Lett 1, 572580 (2010)
  24. Ferrari, A. C. et al. Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 97, 187401187404 (2006)
  25. Chen, J. H. et al. Charge-impurity scattering in graphene. Nature Phys. 4, 377381 (2008)
  26. Zhang, Y. et al. Direct observation of widely tunable bandgap in bilayer graphene. Nature 459, 820823 (2009)
  27. Ci, L. et al. Controlled nanocutting of graphene. Nano Res. 1, 116122 (2008)
  28. Lin, Y. et al. Controllable graphene N-doping with ammonia plasma. Appl. Phys. Lett. 96, 133110 (2010)
  29. Li, X. et al. Simultaneous nitrogen doping and reduction of graphene oxide. J. Am. Chem. Soc. 131, 1593915944 (2009)
  30. Das, A. et al. Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. Nature Nanotechnol. 3, 210215 (2008)
  31. Balog, R. et al. Bandgap opening in graphene induced by patterned hydrogen adsorption. Nature Mater. 9, 315319 (2010)

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Author information

Affiliations

  1. Department of Chemistry, Rice University, 6100 Main Street, Houston, Texas 77005, USA

    • Zhengzong Sun,
    • Zheng Yan,
    • Elvira Beitler,
    • Yu Zhu &
    • James M. Tour
  2. Applied Physics Program, Department of Bioengineering, Rice University, 6100 Main Street, Houston, Texas 77005, USA

    • Jun Yao
  3. Richard E. Smalley Institute for Nanoscale Science and Technology, Department of Mechanical Engineering and Materials Science, Rice University, 6100 Main Street, Houston, Texas 77005, USA

    • James M. Tour

Contributions

Z.S. designed the experiments, discovered the procedures for graphene growth, performed the spectroscopic characterizations and analysis and wrote the manuscript. Z.Y. optimized the growth conditions and contributed to the spectroscopic characterizations. J.Y. performed the electrical measurements and analysis. E.B. contributed to the electrical measurements and analysis. Y.Z. carried out the sheet resistance and transmittance measurements. J.M.T oversaw all research phases and revised the manuscript. All authors discussed and commented on the manuscript.

Competing financial interests

The authors declare no competing financial interests.

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Supplementary information

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  1. Supplementary Information (974K)

    The file contains Supplementary Materials and Methods, Supplementary Figures 1-7 with legends and additional references.

Comments

  1. Report this comment #15962

    Dan Clutter said:

    This is a very interesting paper, however it is not exactly clear what makes this work relevant to Nature and say Nature Nanotechnology/Chemistry/Materials. I can see the widespread implication but as written the work appears more of an exercise in good old fasioned chemistry/chemical engineering. Is it simply because of the popularity of graphene and the promise for a new generation of electronic devices based on this material that make it such a compelling article that publication in Nature is required?

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